EP1516012A1 - Glass fibre reinforced plastics - Google Patents

Abstract

A process for preparing glass fiber reinforced plastics using high-energy radiation. A sizing composition is applied to the glass fiber, and the curing mechanism of the sizing composition proceeds in a controlled way by the use of two crosslinking mechanisms which can be activated separately from one another. Aqueous UV-curing polyurethane dispersions containing few or no active hydrogen atoms are used in combination with water-dispersible or water-soluble blocked polyisocyanates.

Description

 Glass fiber reinforced plastics

The invention relates to a new Nerfaliren for the production of glass fiber reinforced plastics using high-energy radiation.

Aqueous coating compositions based on polyurethane dispersions and blocked polyisocyanates are known. You will e.g. combined to form one-component coating agents. Such coating compositions are used, for example, in the sizing of glass fibers e.g. used for glass fiber reinforced plastics. After application to the glass fibers, the water is first removed. The resulting film (size) is crosslinked by at least partially unblocking and reacting the polyisocyanates it contains. A further reaction of the polyisocyanates contained in the size takes place when the glass fibers are incorporated into plastics. A problem with this procedure is that the deblocking and reaction of the polyisocyanates when sizing the glass fiber and when incorporating it into plastics are difficult to separate from one another, so that process uncertainty results. It is therefore advantageous to use two curing mechanisms that can be activated independently of one another.

The combination of curing by photopolymerization in aqueous coating compositions which contain unsaturated acrylates and post-curing by deblocking polyisocyanates and their crosslinking with polyols is known, for example, from multi-layer coating of automobiles. 01/23453 contain advertising ^• and blocked isocyanate groups in the WO-A to UV radiation and thermally curable aqueous polyurethane dispersions which both UN-curable groups disclosed. The mostly monofunctional acrylate monomers of low molecular weight used, which prevent the build-up of high molecular weight dispersions, are disadvantageous here. Furthermore, so-called reactive diluents, such as multifunctional, low molecular weight, are frequently used to achieve adequate properties Acrylates with sometimes questionable physiological properties added, which also prevent physical drying of the coating.

The object of the present invention was to provide a new process for producing glass fiber-reinforced plastics, the curing mechanism of the size composition being able to run in a controlled manner by means of two crosslinking mechanisms which can be activated separately from one another.

This problem was solved by using aqueous UV-curing polyurethane dispersions that contain little or no active hydrogen atoms in combination with water-dispersible or water-soluble blocked polyisocyanates.

The invention thus relates to a method for producing glass fiber-reinforced plastics, characterized in that a size composition is applied to the glass fiber, the water is removed, and then one

Irradiation with high-energy radiation takes place and in a second step the sized glass fiber is introduced into the plastic and thermal curing is carried out at 150 to 300 ° C. with the release of the polyisocyanate groups by deblocking.

The size composition used in the process according to the invention contains:

(I) at least one water-dispersible or water-soluble blocked polyisocyanate (A),

(II) at least one polyurethane (B) containing free-radically polymerizable groups and containing Zerewitinoff-active hydrogen atoms in groups of from 0 to 0.53 mmol / g, preferably 0 to 0.4 mmol / g, particularly preferably from 0 to 0.25 mmol / g and (III) an initiator (C) which can trigger free-radical polymerization.

For the purposes of the present invention, groups with Zerewitinoff-active H atoms are hydroxyl, primary or secondary amine or thiol groups.

According to the invention, the polyurethanes (B) are in the form of aqueous polyurethane dispersions, emulsions or solutions which are prepared by polyaddition of di- or polyisocyanates (component a) with compounds which are reactive toward isocyanates (components (bl) to (b5)).

Suitable polyisocyanates (a) are aromatic, araliphatic, .aliphatic or cycloaliphatic polyisocyanates. Mixtures of such polyisocyanates can also be used. Examples of suitable polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes or mixtures thereof Isomer content, isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,4 '-Diphenylmethane diisocyanate, triphenylmethane-4,4', 4 "-triisocyanate or their derivatives with urethane, isocyanurate, allophanate, biuret, uretdione, iminooxadiazinedione structure and mixtures thereof. Preferred are hexamethylene diisocyanate, isophorone diisocyanate and isomeric, bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof.

The polyurethane (B) contained in the aqueous coating compositions according to the invention is a reaction product of

(a) one or more di- or polyisocyanates, (b1) one or more compounds having a hydrophilizing action with ionic and / or groups which can be converted into ionic groups and / or nonionic groups,

(b2) one or more compounds with free-radically polymerizable groups,

(b3) optionally one or more polyol compounds with an average molecular weight of 50 to 500, preferably 80 to 200 and a hydroxyl functionality greater than or equal to 2 and less than or equal to 3,

(b4) optionally one or more polyol compounds with an average molecular weight of 500 to 13000 g / mol, preferably 700 to 4000 g / mol with an average hydroxyl functionality of 1.5 to 2.5, preferably from 1.8 to 2.2, particularly preferably from 1.9 to 2.1,

(b5) optionally one or more diamines or polyamines.

Component (bl) contains ionic groups, which can be either cationic or anionic in nature and / or nonionic hydrophilic groups. Cationic, anionic or nonionic dispersing compounds are those which, for example, sulfonium, ammonium, phosphonium, carboxylate, sulfonate, phosphonate groups or the groups which can be converted into the aforementioned groups by salt formation (potentially ionic Groups) or polyether groups and can be built into the macromolecules by existing isocyanate-reactive groups. Suitable isocyanate-reactive groups are preferred

Hydroxyl and amine groups.

Suitable ionic or potentially ionic compounds (bl) are e.g. Mono and

Dihydroxycarboxylic acids, mono- and di-inocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids as well as mono- and dihydroxyphosphonic acids or mono- and diaminophosphonic acids and their salts such as dimethyl lolpropionic acid, dimethylol butyric acid, hydroxypivalic acid, N- (2-aminoethyl) -ß-alanine, 2- (2-amino-ethylamino) -ethanesulfonic acid, ethylenediamine-propyl- or butylsulfonic acid, 1,2- or 1,3-propylenediamine-ß -ethylsulfonsäure. Malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid, an addition product of IPDI and acrylic acid (EP-A 0 916 647,

Example 1) and its alkali and / or ammonium salts; the adduct of sodium bisulfite with butene-2-diol-1,4, polyether sulfonate, the propoxylated adduct of 2-butenediol and NaHSO ₃ , for example described in DE-A 2 446 440 (page 5-9, formula I-III ) and building blocks which can be converted into cationic groups, such as N-methyl-diethanolamine as hydrophilic structural components. Preferred ionic or potentially ionic compounds are those which have carboxy or carboxylate and / or sulfonate groups and / or ammonium groups. Particularly preferred ionic compounds are those which contain carboxyl and / or sulfonate groups as ionic or potentially ionic groups, such as the salts of N- (2-aminoethyl) -ß-alanine, the 2- (2-aminoethylamino) ) ethanesulfonic acid or the addition product of IPDI and acrylic acid (EP-A 0 916 647, Example 1) and dimethylolpropionic acid.

Suitable non-ionically hydrophilizing compounds are e.g. Polyoxyalkylene ethers containing at least one hydroxyl or amino group. This

Polyethers contain from 30% to 100% by weight of building blocks which are derived from ethylene oxide. Linear polyethers with a functionality between 1 and 3 are possible, but also compounds of the general formula

(I)

in which R and R independently of one another each represent a divalent aliphatic, cycloaliphatic or aromatic radical having 1 to 18 carbon atoms, which can be interrupted by oxygen and / or nitrogen atoms, and

q,

R represents an alkoxy-terminated polyethylene oxide radical.

Compounds which have a nonionic hydrophilic action are, for example, monovalent polyalkylene oxide polyether alcohols having a statistical average of 5 to 70, preferably 7 to 55, ethylene oxide units per molecule, as are obtainable in a manner known per se by alkoxylation of suitable starter molecules (for example in Ullmann's Encyclopedia of Industrial Chemistry, 4. Edition, volume 19, Verlag Chemie, Weinheim pp. 31-38).

Suitable starter molecules are, for example, saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n -Hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofirrfuryl alcohol, diethylene glycol monoalkyl ether such as, for example

Diethylene glycol monobutyl ether, unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, aromatic alcohols such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, anis alcohol or cinnamon alcohol, secondary monoamines such as dimethylropylamine, diethylamine, diethylamine , Bis (2-ethylhexyl) amine, N-methyl and N-ethylcyclohexylamine or dicyclohexylamine and heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-pyrazole. Preferred starter molecules are saturated monoalcohols. Diethylene glycol monobutyl ether is particularly preferably used as the starter molecule. Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in the alkoxylation reaction in any order or in a mixture.

The polyalkylene oxide polyether alcohols are either pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers, the alkylene oxide units of which at least 30 mol%, preferably at least 40 mol%, consist of ethylene oxide units. Preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyethers which have at least 40 mol% of ethylene oxide and at most 60 mol% of propylene oxide units.

Component (bl) is preferably a combination of nonionic and ionic hydrophilizing agents. Combinations of nonionic and anionic hydrophilizing agents are particularly preferred.

Component (b2) contains free-radically polymerizable double bonds, preferably hydroxy-functional acrylates or methacrylates. Examples are 2-hydroxyethyl (meth) acrylate, polyethylene oxide mono (meth) acrylates, polypropylene oxide mono- (meth) acrylates, polyalkylene oxide mono (meth) acrylates, poly (ε-caprolactone) mono- (meth) acrylates, such as, for example, ^Tone® M100 (Union Carbide, USA), 2-hydroxypropyl

(meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, the mono-, di- or tetraacrylates of polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxihertes , propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or their technical mixtures. The acrylated monoalcohols are preferred. Also suitable are alcohols which can be obtained from the reaction of acids containing double bonds with monomeric epoxy compounds which may contain double bonds, for example the reaction products of (meth) acrylic acid with glycidyl (meth) acrylate or the glycidyl ester of versatic acid. Furthermore, compounds containing isocyanate-reactive oligomeric or polymeric unsaturated acrylate and / or methacrylate groups can be used alone or in combination with the aforementioned monomeric compounds. Preferred component (b2) are hydroxyl-containing polyester acrylates with an OH content of 30 to 300 mg KOH / g, preferably 60 to 200, particularly preferably 70 to

120 used. A total of 7 groups of monomer components can be used in the preparation of the hydroxy-functional polyester acrylates:

1. (Cyclo) alkanediols such as dihydric alcohols with (cyclo) aliphatic hydroxyl groups in the molecular weight range 62 to 286, e.g. ethanediol,

1,2- and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-l, 4-dimethanol, 1 , 2- and 1,4-cyclohexane diol, 2-ethyl-2-butylpropane diol, diols containing ether oxygen, such as Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene, polypropylene or polybutylene glycols with a molecular weight of 200 to 4000, preferably 300 to 2000, particularly preferably 450 to 1200. Reaction products of the aforementioned diols with ε-caprolactone or other lactones can also are used as diols.

2. Trihydric and higher alcohols in the molecular weight range 92 to 254, such as glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol or polyethers started on these alcohols, such as e.g. the reaction product of 1 mol trimethylolpropane with 4 mol ethylene oxide.

3. Mono alcohols such as Ethanol, 1- and 2-propanol, 1- and 2-butanol, 1-hexanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.

4. dicarboxylic acids of the molecular weight range 104 to 600 and / or their anhydrides, such as, for example, phthalic acid, phthalic anhydride, isophthalic acid, tetra-hydrophthalic acid, tetra-hydrophthalic anhydride, hexahydrophthalic acid, Hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, maleic anhydride, fumaric acid, malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer fatty acids.

5. Highly functional carboxylic acids or their anhydrides such as Trimellitic acid and trimellitic anhydride.

6. monocarboxylic acids, e.g. Benzoic acid, cyclohexane carboxylic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, natural and synthetic fatty acids.

7. Acrylic acid, methacrylic acid or dimeric acrylic acid.

Suitable hydroxyl-containing polyester acrylates contain the reaction product of at least one component from group 1 or 2 with at least one component from group 4 or 5 and at least one component from group 7.

If appropriate, dispersing groups which are generally known from the prior art can also be incorporated into these polyester acrylates. Proportionally, polyethylene glycols and / or methoxypolyethylene glycols can also be used as the alcohol component. Examples of compounds which may be mentioned are polyethylene glycols started on alcohols, polypropylene glycols and their block copolymers, and the monomethyl ethers of these polyglycols. Polyethylene glycol 1500 and / or polyethylene glycol 500 mono-methyl ether is particularly suitable.

It is also possible, after the esterification, to react some of the carboxyl groups, in particular that of (meth) acrylic acid, with mono-, di- or polyepoxides. For example, the epoxides (glycidyl ethers) of monomeric, oligomeric or polymeric bisphenol-A, bisphenol-F, hexanediol and / or butanediol or their ethoxylated and / or propoxylated derivatives are preferred. This reaction can be used in particular to increase the OH number of the polyester (meth) acrylate, since one OH group is formed in each case in the epoxy-acid reaction. The acid number of the resulting product is between 0 and 20 mg KOH / g, preferably between 0 and 10 mg KOH / g and particularly preferably between 0 and 5 mg KOH / g. The reaction is preferred by catalysts such as triphenyphosphine,

Catalyzed thiodiglycol, ammonium and / or phosphorus halides and / or zirconium or tin compounds such as tin (II) ethylhexanoate.

The production of polyester acrylates is described in DE-A 4 040 290 (page 3, line 25 - page 6, line 24), DE-A-3 316 592 (page 5, line 14 - page 4). 11, line 30) and PKT Oldring (Ed.),

Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 2, 1991, SITA Technology, London, pp. 123-135.

Also preferred as component (b2) are the known hydroxyl group-containing epoxy (meth) acrylates with OH contents of 20 to 300 mg KOH / g, preferably 100 to 280 mg KOH / g, particularly preferably 150 to 250 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates with OH contents of 20 to 300 mg KOH / g, preferably from 40 to 150 mg KOH / g, particularly preferably from 50 to 100 mg KOH / g as well as their mixtures with one another and mixtures with unsaturated polyesters containing hydroxyl groups and mixtures with polyester (meth) acrylates or mixtures of unsaturated polyesters containing hydroxyl groups with polyester (meth) acrylates. Such compounds are also described in P.K.T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 2, 1991, SITA Technology, London S 37-56. Epoxy (meth) acrylates containing hydroxyl groups are based in particular on

Reaction products of acrylic acid and / or methacrylic acid with epoxides (glycidyl compounds) of monomeric, oligomeric or polymeric bisphenol-A, bisphenol-F, hexanediol and / or butanediol or their ethoxylated and / or propoxylated derivatives. Suitable low molecular weight polyols (b3) are short-chain, ie. Aliphatic, araliphatic or cycloaliphatic diols or triols containing 2 to 20 carbon atoms. Examples of diols are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentylglycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, positionally isomeric diethyloctanediols, 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1,4-cyclohexanediol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), 2 , 2-Dimethyl-3-hydroxypropionic acid (2,2-dimethyl-3-hydroxypropyl ester). 1,4-Butanediol, 1,4-cyclohexanedimethanol and 1,6-hexanediol are preferred. Examples of suitable triols are trimethylolethane, trimethylolpropane or glycerol; trimethylolpropane is preferred.

Suitable higher molecular weight polyols (b4) are diols or polyols with a number average molecular weight in the range from 500 to 13000 g / mol, preferably 700 to 4000 g / mol. Polymers with an average hydroxyl functionality of 1.5 to 2.5, preferably 1.8 to 2.2, particularly preferably 1.9 to 2.1 are preferred. These include e.g. Polyester alcohols based on aliphatic, cycloaliphatic and / or aromatic di-, tri- and / or polycarboxylic acids with di-, tri-, and / or polyols as well as polyester alcohols based on lactone. Preferred polyester alcohols are e.g. Reaction products of adipic acid with hexanediol, butanediol or neopentyl glycol or mixtures of the diols mentioned with a molecular weight of 500 to 4000, particularly preferably 800 to 2500. Also suitable are polyetherols which can be obtained by polymerizing cyclic ethers or by reacting alkylene oxides with a starter molecule , Examples include the polyethylene and / or polypropylene glycols with an average molecular weight of 500 to 13000, furthermore polytetrahydrofurans with an average molecular weight of 500 to 8000, preferably from 800 to 3000. Also suitable are hydroxyl-terminated polycarbonates which are obtained by reacting Diols or lactone-modified diols or bisphenols, such as Bisphenol A, with phosgene or carbonic acid diesters such as diphenyl carbonate or dimethyl carbonate.

The polymeric carbonates of 1,6-hexanediol of a medium- Ren molecular weight of 500 to 8000, and the carbonates of reaction products of 1,6-hexanediol with ε-caprolactone in a molar ratio of 1 to 0.1. Preference is given to the aforementioned polycarbonate diols having an average molecular weight of 800 to 3000 based on 1,6-hexanediol and / or carbonates of reaction products of 1,6-hexanediol with ε-caprolactone in a molar ratio of 1 to 0.33.

Hydroxyl-terminated polyamide alcohols and hydroxyl-terminated polyacrylate, eg Tegomer® ^® BD 1000 (Fa. Tego GmbH, Essen, DE) are also used.

Component (b5) is selected from the group of di- and / or polyamines which are used to increase the molar mass and are preferably added towards the end of the polyaddition reaction. This reaction preferably takes place in an aqueous medium. Then the di- and / or polyamines must be more reactive than water to the isocyanate groups of component (a). Examples include ethylenediamine, 1,3-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, 1,3-, 1,4-phenylenediamine, 4,4'-diphenylmethane diamine, amino-functional polyethylene oxides or polypropylene oxides, which are sold under the name Jeffamin ^® , D series (from Huntsman Corp. Europe, Belgium) are available, diethylenetriamine, triethylenetetraamine and hydrazine. Isophoronediamine, ethylenediamine, 1,6-hexamethylenediamine are preferred. Ethylene diamine is particularly preferred.

Proportionally it is also monoamines such as butylamine, ethylamine and amines of the Jeffamin ^® M series (Huntsman Corp. Europe, Belgium), amino-functional poly ethylene oxides and polypropylene oxides are added.

The polyurethane (B) can be prepared in one or more stages in a homogeneous phase or, in the case of a multi-stage reaction, in part in the disperse phase. After the polyaddition has been carried out in full or in part, a dispersing, emulsifying or dissolving step takes place. This may be followed by a further polyaddition or modification in the disperse phase. All processes known from the prior art, such as emulsifier-shear force, acetone, prepolymer mixing, melt-emulsifying, ketimine and solid-spontaneous dispersion processes, or descendants thereof, can be used to produce the polyurethane (B) become. A summary of these methods can be found in methods of organic chemistry (Houben-Weyl, extension and

Subsequent volumes to the 4th edition, volume E20, H. Bartl and J. Falbe, Stuttgart, New York, Thieme 1987, pp. 1671 - 1682). The melt emulsification and acetone processes are preferred. Acetone V is particularly preferred.

Components (b1) to (b5) which have no primary or secondary amino groups and a polyisocyanate (a) for the preparation of a polyurethane prepolymer are usually initially or completely introduced into the rector and, if appropriate, diluted with a water-miscible solvent which is inert to isocyanate groups , but preferably without solvent, heated to higher temperatures, preferably in the range from 50 to 120 ° C.

Suitable solvents are e.g. Acetone, butanone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether and l-methyl-2-pyrrolidone, which can be added not only at the start of the production but also, if necessary, in part later. Acetone and butanone are preferred. It is possible to take the reaction below

Normal pressure or increased pressure, e.g. above the normal pressure boiling temperature of an optionally added solvent, such as Acetone.

Furthermore, the catalysts known to accelerate the isocyanate addition reaction, e.g. Triethylamine, l, 4-diazabicyclo- [2,2,2] octane, tin dioctoate or dibutyltin dilaurate are initially introduced or added later. Dibutyltin dilaurate is preferred.

Subsequently, the constituents (a) and / or (bl) to (b4) which have not yet been added at the start of the reaction and which are not primary or secondary

Amino groups have added. In the manufacture of the polyurethane prepolymer The molar ratio of isocyanate groups to isocyanate-reactive groups is 0.90 to 3, preferably 0.95 to 2, particularly preferably 1.05 to 1.5. The reaction of components (a) with (b) takes place, based on the total amount of isocyanate-reactive groups of the portion of (b) which has no primary or secondary amino groups, partially or completely, but preferably completely. The degree of conversion is usually monitored by monitoring the NCO content of the reaction mixture. For this purpose, both spectroscopic measurements, for example infrared or near-infrared spectra, determinations of the refractive index as well as chemical analyzes, such as titrations, of samples taken can be carried out. Polyurethane prepolymers containing free isocyanate groups are obtained in bulk or in solution.

After or during the yeast preparation of the polyurethane prepolymers from (a) and (b), if this has not yet been carried out in the starting molecules, the partial or complete salt formation of the anionically and / or cationically dispersing groups takes place. In the case of anionic groups, bases such as ammonia, ammonium carbonate or hydrogen carbonate, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, dimethylethanolamine, diethylethanolamine, triethanolamine, potassium hydroxide or sodium carbonate are used, preferably triethylamine, triethanolamine, dimethylethanolamine or diisopropylamine. The

The amount of the base is between 50 and 100%, preferably between 60 and 90% of the amount of the anionic groups. In the case of cationic groups, dimethyl sulfuric acid or succinic acid are used. If only non-ionically hydrophilized compounds (bl) with ether groups are used, the neutralization step is omitted. The neutralization can also take place at the same time as the dispersion, in which the dispersing water already contains the neutralizing agent.

The possibly remaining isocyanate groups are reacted by reaction with amine components (b5) and / or, if present, amine components (b1). This chain extension can be carried out either in solvent before dispersion or in water after dispersion. are contain aminic components (bl), the chain extension is preferably carried out before the dispersion.

The di- or polyamines (b5) and / or if present the amine component (bl) can be added to the reaction mixture diluted with organic solvents and / or with water. 70 to 95% by weight of solvent and / or water are preferably used. If several amine components (bl) and / or (b5) are present, the reaction can be carried out successively in any order or simultaneously by adding a mixture.

For the preparation of the polyurethane dispersion (B), the polyurethane prepolymers are used, optionally with strong shear, such as e.g. vigorous stirring, either introduced into the dispersing water or, conversely, the dispersing water is stirred into the prepolymers. Then, if it has not yet occurred in the homogeneous phase, the molar mass can be increased by reacting any isocyanate groups present with component (b5). The amount of polyamine (b5) used depends on the unreacted isocyanate groups still present. 50 to 100%, particularly preferably 75 to 95% of the amount of the isocyanate groups are preferably reacted with polyamines (b5).

The resulting polyurethane-polyurea prepolymers have an isocyanate content of 0 to 2% by weight, preferably 0 to 0.5% by weight.

If appropriate, the organic solvent can be distilled off. The dispersions have a solids content of 20 to 70% by weight, preferably 30 to 65

Wt .-%. The non-volatile fractions of these dispersions have a content of chemical groups containing Zerewitinoff active hydrogen atoms of 0 to 0.53 mmol / g, preferably 0 to 0.4 mmol / g, particularly preferably 0 to 0.25 mmol / g , Suitable blocked polyisocyanates (A) which are contained in the size compositions to be used according to the invention are water-dispersible or water-soluble blocked polyisocyanates.

Suitable water-dispersible or water-soluble blocked polyisocyanates (A) are obtained by reacting

(AI) at least one polyisocyanate with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups,

(A2) at least one ionic or potentially ionic and / or nonionic compound,

(A3) at least one blocking agent,

(A4) optionally one or more (cyclo) aliphatic mono- or polyamines with 1 to 4 amino groups in the molecular weight range 32 to 300,

(A5) optionally one or more polyhydric alcohols with 1 to 4 hydroxyl groups in the molecular weight range 50 to 250 and

(A6) optionally one or more compounds containing isocyanate-reactive and unsaturated groups.

The polyisocanates (A) can optionally stabilizers (A7) and others

Contain auxiliaries and optionally solvents (A8).

The water-dispersible or water-soluble blocked polyisocyanates (A) are composed of 20 to 80% by weight, preferably 25 to 75% by weight, particularly preferably 30 to 70% by weight of component (AI), 1 to 40% by weight, preferably 1 to 35% by weight, particularly preferably 5 to 30% by weight of component (A2), 15 to 60% by weight, preferably 20 to 50% by weight, particularly preferably 25 to 45% by weight of component (A3), 0 to 15% by weight, preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight of Component (A4), 0 to 15% by weight, preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight of component (A5), 0 to 40% by weight, preferably 0% by weight of the Component (A6) and 0 to 15% by weight, preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight of component (A7) and optionally 0 to 20% by weight, preferably 0 to 15 % By weight, particularly preferably 0 to 10% by weight of component (A8), the sum of the components adding up to 100% by weight.

The water-dispersible or water-soluble blocked polyisocyanates (A) can be used in the coating compositions as an aqueous solution or dispersion. The solution or dispersion of the polyisocyanates has a solids content of between 10 to 70% by weight, preferably from 20 to 60% by weight and particularly preferably from 25 to 50% by weight, and the proportion of (A8) in the total The composition is preferably less than 15% by weight and particularly preferably less

10% by weight and very particularly preferably less than 5% by weight.

The polyisocyanates (Al) used to prepare the blocked polyisocyanates (A) have an (average) NCO functionality of 2.0 to 5.0, preferably 2.3 to 4.5, and an isocyanate group content of 5.0 to 27.0% by weight, preferably of

14.0 to 24.0% by weight and a content of monomeric diisocyanates of less than 1% by weight, preferably less than 0.5% by weight. The isocyanate groups of the polyisocyanates (Al) are at least 50%, preferably at least 60% and particularly preferably at least 70% in blocked form.

Suitable polyisocyanates (AI) for the preparation of the blocked polyisocyanates (A) are the polyisocyanates prepared from at least two diisocyanates and containing uretdione, isocyanurate, allophanate and biuret polyisocyanates prepared by modifying simple aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates. , Iminooxadiazinedione and / or oxadiazinetrione structure, as described, for example, in J. Prakt. Chem. 336 (1994) page 185-200 are described by way of example. Suitable compounds for component (A2) are ionic or potentially ionic and / or nonionic compounds as have already been described under component (bl).

Component (A2) is preferably a combination of nonionic and ionic hydrophilizing agents. Combinations of nonionic and anionic hydrophilizing agents are particularly preferred.

Examples of blocking agents (A3) include: alcohols, lactams, oximes,

Malonic esters, alkylacetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines, such as e.g. Butanone oxime, diisopropylamine, 1,2,4-triazole, dimethyl-l, 2,4-triazole, imidazole, diethyl malonate, acetoacetic ester, acetone oxime, 3,5-dimethylpyrazole, ε-caprolactam, N-tert-butyl-benzylamine or any other Mixtures of these blocking agents. Butanone oxime, 3,5-dimethylpyrazole, ε-caprolactam,

N-tert-butyl-benzylamine used as a blocking agent (A3). Particularly preferred blocking agents (A3) are butanone oxime and ε-caprolactam.

Possible components (A4) are mono-, di-, tri- and / or teixa-amino-functional substances of the molecular weight range up to 300, such as Ethylenediamine, 1,2- and 1,3-diaminopropane, 1,3-, 1,4- and 1,6-diaminohexane, 1,3-diamino-2,2-dimethylpropane, 1 - amino-3, 3, 5 -trimethyl-5-aminoethyl-cyclohexane (IPD A), 4,4'-diaminodicyclohexylmethane, 2,4- and 2,6-diamino-l-methyl-cyclohexane, 4,4 '- diamino-3, 3'-dimethyl -dicyclohexylmethane, 1, 4-bis- (2-amino-prop-2-yl) -cyclohexane or mixtures of these compounds.

Component (A5) is mono-, di-, tri- and / or tetra-hydroxy-functional substances with a molecular weight of up to 250, e.g. Ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediols, glycerol, trimethylolethane, trimethylolpropane, the isomeric hexanetriols, pentaerythritol or mixtures thereof

Links. As component (A6), hydroxy-functional and (meth) acrylic-functional compounds are reacted with the isocyanates. Such compounds are described, for example, as components of component (b2) above. Compounds with an average hyoxy functionality of 0.2 to 2, particularly preferably 0.7 to 1.3, are preferred. Particularly preferred are 2-hydroxyethyl (meth) acrylate, poly (ε-caprolactone) monoacrylates, such as Tone Ml 00 ^® (Union Carbide, USA), pylacrylat 2-hydroxypropyl, 4-hydroxybutyl acrylate, trimethylolpropane diacrylate, glycerol diacrylate, pentaerythritol triacrylate or dipentaerythritol.

The blocked polyisocyanates (A) can optionally contain a stabilizing agent or stabilizing agent mixture (A7). Suitable compounds (A7) are e.g. Antioxidants such as 2,6-ditert-butyl-4-methylphenol, UV absorbers of the 2-hydroxyphenyl-benzotriazole type or light stabilizers of the HALS compound type or other commercially available stabilizers, as described, for example, in

"Light stabilizers for paints" (A. Valet, Vincentz Verlag, Hanover, 1996,) and "Stabilization of Polymeric Materials" (H. Doubt, Springer Verlag, Berlin, 1997, Appendix 3, pp. 181-213) are described.

Mixtures of stabilizers which contain compounds with a 2,2,6,6-

Tetramethylpiperidinyl residue, (HALS) have. The piperidinyl nitrogen of the HALS ring is not substituted and has no hydrazide structures. A compound of the formula (II) is particularly preferred

which is sold, for example, under the name Tinuvin ^® 770 ^' DF by the company Ciba specialties (Lampertheim, DE).

Ideally, the above Compounds combined with substances that have hydrazide structures, such as acid hydrazides and dihydrazides, e.g. Acetic acid hydrazide, adipic acid hydrazide, adipic acid dihydrazide or hydrazine adducts of hydrazine and cyclic carbonates, as they are mentioned, for example, in EP-A 654 490 (page 3, line 48 to page 4 line 3). Preference is given to adipic acid dihydrazide and an adduct of 2 mol of propylene carbonate and 1 mol of hydrazine of the general formula (HI)

-CO-NH-NH- (III) used.

The adduct of 2 mol of propylene carbonate and 1 mol of hydrazine of the general formula (IV) is particularly preferred:

Suitable organic solvents (A8) are the conventional lacquer solvents, such as ethyl acetate, butyl acetate, 1-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, Cyclohexanone, toluene, xylene, chlorobenzene or white spirit. Mixtures, especially higher-substituted aromatics include, as for example, under the names Solvent Naphtha, sol Vesso ^® (Exxon Chemicals, Houston, USA), Cypar ^® (Shell Chemicals, Eschborn,

DE), Cyclo Sol ^® (Shell Chemicals, Eschborn, DE), Tolu Sol ^® (Shell Chemicals, Eschborn, DE), Shellsol ^® (Shell Chemicals, Eschborn, DE) are commercially available, are also suitable. Other solvents are, for example, carbonic acid esters, such as Dimethyl carbonate, diethyl carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate, lactones, such as ß-propiolactone, γ-butyrolactone, ε-caprolactone, ε-methylcaprolactone, propylene glycol kiacodiacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl acetate and butyl butyl N-methylpyrrolidone and N-methylcaprolactam or any mixture of such solvents. preferred

Solvents are acetone, 2-butanone, l-methoxypropyl-2-acetate, xylene, toluene, mixtures containing mainly highly substituted aromatics such as, for example, under the names Solvent Naphtha, Solvesso ^® (Exxon Chemicals, Houston, USA), Cypar ^® (Shell Chemicals, Eschborn, DE), cyclo Sol ^® (Shell Chemicals, Eschborn, DE), Tolu Sol ^® (Shell Chemicals, Eschborn, DE),

Shellsol ^® (Shell Chemicals, Eschborn, DE) are commercially available, and N-methylpyrrolidone. Acetone, 2-butanone and N-methylpyrrolidone are particularly preferred.

The blocked polyisocyanates (A) can be prepared by known methods of the prior art (e.g. in DE-A 2 456 469, columns 7-8, examples 1-5 and

DE-A 2 853 937 pp. 21-26, example 1-9).

The water-dispersible or water-soluble blocked polyisocyanates (A) can be reacted, for example, by reacting components (AI), (A2), (A3) and, if appropriate, (A4) to (A7) in any order, if appropriate with the aid of an organic solvent (A8) become.

It is preferred first to react (AI) with, if appropriate, part, preferably the nonionic part of component (A2) and, if appropriate, (A4) and (A5). This is followed by blocking with component (A3) and then reaction with the part of component (A2) containing ionic groups. If appropriate, organic solvents (A8) can be added to the reaction mixture. In a further step, component (A7) is optionally added. The aqueous solution or dispersion of the blocked polyisocyanates (A) is then prepared by converting the water-dispersible blocked polyisocyanates into an aqueous dispersion or solution by adding water. The organic solvent (A8) which may be used can be removed by distillation after the dispersion. Preference is given to the

No use of solvent (A8).

The aforementioned water-dispersible or water-soluble blocked polyisocyanates can also contain unsaturated groups capable of radical polymerization. For this purpose, the polyisocyanates can be dispersed, emulsified or

Dissolving in water is first partially blocked and then reacted with compounds (A6) containing isocyanate-reactive and unsaturated groups, or the polyisocyanates are first reacted with compounds (A6) containing isocyanate-reactive and unsaturated groups and then with blocking agents (A3).

For the preparation of the aqueous solution or dispersion of the blocked polyisocyanates (A), such amounts of water are generally used that the resulting dispersions have a solids content of 10 to 70% by weight, preferably 20 to 60% by weight and particularly preferably 25 have up to 50 wt .-%.

Initiators (C) for radical polymerization can be initiators which can be activated by radiation and / or thermally activated. Photo initiators that are activated by UV or visible light are preferred. Photoinitiators are commercially known compounds known per se, a distinction being made between unimolecular (type I) and bimolecular (type II) initiators.

Suitable (Type I) systems are such as aromatic ketone compounds, e.g. Benzophenones in combination with tertiary amines, alkylbenzophenones, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone and halogenated benzophenones or mixtures of the types mentioned. Also suitable are (type II) initiators such as benzoin and its derivatives, benzil ketals, acylphosphine oxides e.g.

2,4,6-trimethyl-berιzoyl-diphenylphosphine oxide, bisacylphosphine oxides, phenylgly- oxylic acid esters, camphorquinone, α-aminoalkylphenones, α, α-diaxoxyacetophenones and α-hydroxyalkylphenones. Photoinitiators that can be easily incorporated into aqueous coating compositions are preferred. Such products include Irgacure ^® 500, Irgacure ^® 819 DW (Messrs. Ciba, Lampertheim, DE), Esacure ^® KTP (Fa. Lamberti, Aldizzate, Italy). Mixtures of these compounds can also be used.

If the curing is initiated thermally, peroxy compounds such as diacyl peroxides are suitable e.g. Benzoyl peroxide, alkyl hydroperoxides such as diisopropylbenzene monohydroperoxide, alkyl peresters such as tert-butyl perbenzoate, dialkyl peroxides such as di-tert-butyl peroxide, peroxidicarbonates such as dicetyl peroxide dicarbonate, inorganic peroxides such as arnmonium peroxodisulfate, potassium peroxodisulfobis (or also 2-propenyl) -2-methylpropionamide], l - [(cyano-l-methylethyl) azo] formamide, 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N. -cyclohexyl-2-methylpropionamide), 2,2'-azobis {2-methyl-N- [2- (l-hydroxybutyl)] propionamide}, 2,2'-azobis {2-methyl-N- [2 - (l-Hydroxybutyl)] ρropionamide, 2,2'-azobis {2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide, furthermore also benzpinacol. Compounds which are water-soluble or are present as aqueous emulsions are preferred. These radical formers can be combined with accelerators in a known manner.

To prepare the aqueous size composition, the constituents (I), (II) and (III) are mixed with one another in any order or simultaneously. The aqueous coating agents have no pot life and are stable for months or longer.

For the process according to the invention, the aqueous size composition is used alone or, if appropriate, with further binders such as, for example, polyurethane dispersions, polyacrylate dispersions, polyurethane-polyacrylate hybrid dispersions, polyvinyl ether or polyvinyl ester dispersions, polystyrene or polyacrylonitrile dispersions. ions, also in combination with other blocked polyisocyanates and amino crosslinking resins such as melamine resins.

The size composition can contain the usual auxiliaries and additives, e.g. Defoamers, thickeners, leveling agents, dispersing aids, catalysts, skin-preventing agents, anti-settling agents, antioxidants, plasticizers, reactive thinners, emulsifiers, biocides, adhesion promoters, e.g. based on the known low or high molecular weight silanes, lubricants, wetting agents, antistatic agents.

As adhesion promoters e.g. the known silane coupling agent used, for example 3-aminopropyltrimethoxy or triethoxysilane, N- (2-aminoethyl) -3- aminopropyltrimethoxy silane, 3-glycidylpropyltrimethoxy silane, vinyltrimethoxysilane, vinyltriethoxysilane or 3-methacryloxypropyltriethoxysilane. The concentration of the silane coupling agents in the layering agents according to the invention is preferably 0.05 to 2% by weight, particularly preferably 0.15 to 0.85% by weight, based on the overall size.

The sizes contain one or more nonionic and / or ionic lubricants, which e.g. can consist of the following groups of substances: polyalkylene glycol ethers of fatty alcohols or fatty amines, polyalkylene glycol ethers and glycerol esters of fatty acids with 12 to 18 carbon atoms, polyalkylene glycols, higher fatty acid amides with 12 to 18 carbon atoms of polyalkylene glycols and / or alkylene amines, quaternary nitrogen compounds, e.g. ethoxylated imidazolinium salts, mineral oils and waxes. The lubricant or lubricants are preferably used in the total concentration between 0.05 and 1.5% by weight, based on the total size.

The sizes can be one or more antistatic agents, such as lithium chloride, ammonium chloride, Cr III salts, organic titanium compounds, arylalkyl sulfate or sulfonates, aryl polyglycol ether sulfonates or quaternary nitrogen compounds, contain. The antistatic agents are preferably used in concentrations of 0.01 to 0.8% by weight.

In addition, the sizes optionally contain further auxiliaries and additives known from the prior art, as described, for example, in K.L.

Loewenstein "The Manufacturing Technology of Continuous Glass Fibers", Elsevier

Scientific Publishing Corp., Amsterdam, London, New York, 1983.

The sizes can be produced using the methods known per se. Approximately half of the total water required is preferably placed in a suitable mixing container and the binder, the hardener and then the lubricant 4) and, if appropriate, other customary auxiliaries are added with stirring. Then the pH is adjusted to 5-7 and hydrolyzate of an adhesion promoter, e.g. manufactured according to the manufacturer (e.g. UCC, New York), is produced. a trialkoxysilane added. After a further stirring time of 15 minutes, the

Simple ready to use; if necessary, the pH is adjusted again to 5-7.

The sizes can be applied to the glass fiber by any method, for example with the aid of suitable devices, such as Spray or roller applicators.

Suitable glass fibers are both the known glass types used for glass fiber production, such as E, A, C and S glass, and also the other known products from glass fiber manufacturers. E-glass fibers are preferred which are used for the production of continuous glass fibers due to their freedom from alkali, high tensile strength and high modulus of elasticity for the reinforcement of plastics.

The process for the production, the process of sizing and the post-processing of the glass fibers is known and is described, for example, in KL Loewenstein “The Manufacturing Technology of Continous Glass Fibers ", Elsevier Scientific Publishing Corp., Amsterdam, London, New York, 1983.

Usually, the sizes are applied to the glass filaments drawn at high speed from spinning nozzles immediately after they have solidified, i.e. applied before winding up. However, it is also possible to size the fibers in an immersion bath after the spinning process. The sized glass fibers can be processed either wet or dry, for example into chopped glass. The end or intermediate product is dried by irradiation with high-energy radiation, preferably ultraviolet light and / or by heating

Temperatures between 50 to 200 ° C, preferably 70 to 150 ° C instead. Drying is not only to be understood as the removal of other volatile components, but e.g. also the setting of the size components. Only after the drying process has been completed has the size changed into the finished coating compound. The proportion of the size, based on the sized glass fibers, is preferably 0.1 to 5.0% by weight, particularly preferably 0.1 to 3.0% by weight and very particularly preferably 0.3 to 1.5% by weight .-%.

Drying of the sized glass fiber preferably takes place in several stages: first, heat, convection, heat radiation and / or dehumidification

Air water and any solvent removed from the size. Then the curing takes place by UV radiation. The usual spotlights according to the state of the art are used. High-pressure or medium-pressure mercury lamps, which can optionally be doped with elements such as gallium or iron, are preferred. It can also be useful to have several

Combine spotlights one behind the other, side by side or in any three-dimensional arrangement. Furthermore, it may be expedient to carry out the UV radiation at elevated temperatures, at 30 to 200 ° C.

The sized glass fibers can then be incorporated into matrix polymers. A large number of thermoplastics or thermosetting polymers can be used as matrix polymers. For example, the following are suitable as thermoplastic polymers: polyolefins such as polyethylene or polypropylene, polyvinyl chloride, polymers such as styrene / acrylonitrile copolymers, ABS, polymethacrylate or

Polyoxymethylene, aromatic and / or aliphatic polyamides such as polyamide-6 or polyamide-6,6, polycondensates such as polycarbonate, polyethylene terephthalate, liquid-crystalline polyaryl esters, polyarylene oxide, polysulphone, polyarylene sulphide, polyaryl sulphone, polyether sulphone, polyaryl ether or polyether ketone or polyadducts. Examples of thermosetting polymers are:

Epoxy resins, unsaturated polyester resins, phenolic resins, primary resins, polyurethane resins, polyisocyanurates, epoxy-isocyanurate combination resins, furan resins, cyanurate resins and bismaleimide resins.

The incorporation into the polymer matrix can be carried out according to the generally customary

Fachmaim, known methods (such as extrusion). Temperatures of between 150 and 300 ° C. are usually reached here, which leads to thermal post-curing of the size with the release of the polyisocyanate groups by deblocking and, if appropriate, crosslinking them with the polymer matrix.

Examples:

UN PU dispersions

Example 1:

Preparation of a polyester acrylate la) analogous to DE-C 197 15 382 (p. 5 lines 21-27), OH number: 160 mg KOH / g, acid number: 1 mg KOH / g, viscosity: 0.5 Pa s at 23 ° C.

Production of a polyurethane dispersion

298.0 g of the polyester acrylate la) and 27.0 g of the polyether LB 25 (Bayer AG, DE, monofunctional polyether based on ethylene oxide / propylene oxide with a.) Are placed in a reaction vessel with a stirrer, internal thermometer and gas inlet (air flow 1 l / h) average molecular weight of 2250 (OHZ = 25)) submitted and melted. After addition of 168.6 g Isophorondusocyanat (Desmodur I ^®, Bayer AG, DE) and 170.0 g of acetone, the reaction mixture is heated to reflux temperature. The mixture is stirred at this temperature until the reaction mixture has an NCO content of 3.6-3.8% by weight. When the NCO content is reached, the prepolymer is dissolved in 350.0 g of acetone and adjusted to 40 ° C.

Then a solution of 9.9 g of ethylenediamine, 47.5 g of 45% strength AAS solution (2- (2-aminoethylamino)) ethanesulfonic acid, in water, Bayer AG, Leverkusen, DE) and 67.6 g of water in 2 min. added and 5 min. stirred. Then 692.8 g of water are within 10 min. added. The dispersion formed is stirred further at 40 ° C. until no more NCO content can be detected in the dispersion by IR spectroscopy.

The product is distilled in a vacuum at temperatures below 50 ° C until a solids content of 39% is reached. The dispersion has a pH of 7.0 and a average particle size of 86 nm (laser correlation spectroscopy measurement: Zetasizer 1000, Malvern histruments, Malvern, UK).

Example 2: Preparation of a polyurethane dispersion

298.0 g of polyester acrylate la), 27.0 g of polyether LB 25 (Bayer AG, DE, monofunctional polyether based on ethylene oxide / propylene oxide with a medium one) are placed in a reaction vessel with stirrer, internal thermometer and gas inlet (air flow 1 l / h) Molecular weight of 2250 (OHZ = 25)) submitted and melted. After addition of 168.6 g Isophorondusocyanat (Desmodur I ^®, Bayer AG, DE) and 170.0 g of acetone, the reaction mixture is heated to reflux temperature. The mixture is stirred at this temperature until the reaction mixture has an NCO content of 4.2-4.4% by weight. When the NCO content is reached, the prepolymer is dissolved in 350.0 g of acetone and adjusted to 40 ° C.

Then a solution of 11.4 g of ethylenediamine, 36.9 g of 45% AAS solution (2- (2-aminoethylamino)) ethanesulfonic acid, in water, Bayer AG, Leverkusen, DE) and 63.7 g of water in 2 min. added and 5 min. stirred. Then 698.5 g of water within 10 min. added. The dispersion formed is stirred further at 40 ° C. until no more NCO content can be detected in the dispersion by IR spectroscopy.

The product is distilled in a vacuum at temperatures below 50 ° C until a solids content of 39% is reached. The dispersion has a pH of 6.6 and an average particle size of 113 nm (laser correlation spectroscopy measurement: Zetasizer 1000, Malvern Instruments, Malvern, UK). Example 3:

Production of a polyurethane dispersion

In a reaction vessel with stirrer, internal thermometer and gas inlet (air flow 1 l / h) 298.0 g of the polyester acrylate la), 27.0 g of the polyether LB 25 (Bayer

AG, DE, monofunctional polyether based on ethylene oxide-Z propylene oxide with an average molecular weight of 2250 (OHZ = 25)) and melted. After addition of 168.6 g Isophorondusocyanat (Desmodur I ^®, Bayer AG, DE) and 170.0 g of acetone, the reaction mixture is heated to reflux temperature. The mixture is stirred at this temperature until the reaction mixture has an NCO

Contains content of 4.2 - 4.4 wt .-%. When the NCO content is reached, the prepolymer is dissolved in 350.0 g of acetone and adjusted to 40 ° C.

Then a solution of, 12.1 g of ethylenediamine, 31.7 g of 45% AAS solution (2- (2-aminoethylamino)) ethanesulfonic acid, in water, Bayer AG, Leverkusen, DE) and

61.7 g water in 2 min. added and 5 min. stirred. Then 700.9 g of water within 10 min. added. The dispersion formed is stirred further at 40 ° C. until no more NCO content can be detected in the dispersion by IR spectroscopy.

The product is distilled in vacuo at temperatures below 50 ° C until a solids content of 39% is reached. The dispersion has a pH of 6.8 and an average particle size of 83 nm (laser correlation spectroscopy measurement: Zetasizer 1000, Malvern Instruments, Malvern, UK).

Example 4:

Production of a polyurethane dispersion

139.0 g of the polyester PE 170 HN (ester based on adipic acid, 1,6-hexanediol, neopentyl glycol, MW = 1700, Bayer) are placed in a reaction vessel with a stirrer, internal thermometer and gas inlet (air flow 1 l / h) AG, Leverkusen, DE), 238.5 g of the polyester acrylate la), 27.0 g of the polyether LB 25 (Bayer AG, Leverkusen, DE, monofunctional polyether based on ethylene oxide-Z-propylene oxide with an average molecular weight of 2250 (OHZ = 25)) and melted. After addition of 168.6 g Isophorondusocyanat (Desmodur I ^®, Bayer AG, Lev., DE) and 170.0 g of acetone, the. Reaction mixture is heated to reflux temperature. The mixture is stirred at this temperature until the reaction mixture has an NCO content of 3.6-3.8% by weight. When the NCO content is reached, the prepolymer is dissolved in 350.0 g of acetone and adjusted to 40 ° C.

Then a solution of 11.4 g of ethylenediamine, 36.9 g of 45% AAS solution (2-

(2-aminoethylamino) ethanesulfonic acid, in water, Bayer AG, Leverkusen, DE) and 63.7 g of water in 2 min. added and 5 min. stirred. Then 817.7 g of water within 10 min. added. The dispersion formed is stirred further at 40 ° C. until no more NCO content can be detected in the dispersion by IR spectroscopy.

The product is distilled in vacuo at temperatures below 50 ° C until a solid of 40% is reached. The dispersion has a pH of 6.8 and an average particle size of 83 nm (laser correlation spectroscopy measurement: Zetasizer 1000, Malvern Instruments, Malvern, UK).

Example 5:

Production of a polyurethane dispersion

278.0 g of the PE 170 HN polyester (ester based on adipic acid, 1,6-hexanediol, neopentyl glycol, MW = 1700, Bayer AG, Leverkusen, DE), 179.0 g of the polyester acrylate la), 27.0 g of the polyether LB 25 (Bayer AG, Lev., DE, monofunctional polyether based on ethylene oxide / propylene oxide with an average molecular weight of 2250 (OHZ = 25)) and 170.0 g acetone will

Reaction mixture heated to reflux temperature. It will be this long The temperature was stirred until the reaction mixture had an NCO content of 3.3-3.5% by weight. When the NCO content is reached, the prepolymer is dissolved in 350.0 g of acetone and adjusted to 40 ° C.

Then a solution of 11.4 g of ethylenediamine, 36.9 g of 45% AAS solution (2-

(2-aminoethylamino) ethanesulfonic acid, in water, Bayer AG, Leverkusen, DE) and 63.7 g of water in 2 min. added and 5 min. stirred. Then 936.9 g of water within 10 min. added. The dispersion formed is stirred further at 40 ° C. until no more NCO content can be detected in the dispersion by IR spectroscopy.

The product is distilled in vacuo at temperatures below 50 ° C until a solid of 40% is reached. The dispersion has a pH of 6.7 and an average particle size of 176 nm (laser correlation spectroscopy measurement: Zetasizer 1000, Malvern Instruments, Malvem, UK).

Example 6:

Production of a polyurethane dispersion

418.0 g of the PE 170 HN polyester (ester based on adipic acid, 1,6-hexanediol, neopentyl glycol, MW = 1700, Bayer AG, Leverkusen, DE), 119.0 g of the polyester acrylate la), 27.0 g of the LB 25 polyether (Bayer AG, Lev., DE, monofunctional polyether based on ethylene oxide / propylene oxide with an average molecular weight of 2250 (OHZ = 25)) presented and melted. To

Addition of 168.6 g Isophorondusocyanat (Desmodur I ^®, Bayer AG, Lev., DE) and 170.0 g of acetone is heated the reaction mixture to reflux temperature. The mixture is stirred at this temperature until the reaction mixture has an NCO content of 3.0-3.2% by weight. When the NCO content is reached, the prepolymer is dissolved in 350.0 g of acetone and adjusted to 40 ° C. Then a solution of 11.4 g of ethylenediamine, 36.9 g of 45% AAS solution (2- (2-aminoethylamino)) ethanesulfonic acid, in water, Bayer AG, Leverkusen, DE) and 63.7 g of water in 2 min. added and 5 min. stirred. 1057.2 g of water are then added within 10 min. added. The dispersion formed is stirred further at 40 ° C. until no more NCO content can be detected in the dispersion by IR spectroscopy.

The product is distilled in vacuo at temperatures below 50 ° C until a solid of 40% is reached. The dispersion has a pH of 6.7 and an average particle size of 192 nm (laser correlation spectroscopy measurement:

Zetasizer 1000, Malvern Instruments, Malvern, UK).

Water-dispersible blocked polyisocyanates (A)

Example 7:

108.4 g of a biuret group-containing polyisocyanate based on 1,6-diisocyanate hexane (HDI) with an NCO content of 23.0% is placed at 40 ° C. Within 10 min. 91.1 g of polyether LB 25 (Bayer AG, Lev., DE, monofunctional polyether based on ethylene oxide / propylene oxide with an average molecular weight of 2250 (OHZ = 25) and 1.2 g of the above-mentioned hydrazine adduct from 1 mol of hydrazine hydrate and 2 mol of propylene carbonate of molecular weight 236 of the formula (III) are metered in with stirring, then the reaction mixture is heated to 90 ° C. and stirred at this temperature until the theoretical NCO value is reached min. 88.3 g of N-tert-butylbenzylamine, with stirring, added dropwise such that the temperature of the mixture does not exceed 70 ° C. 1.5 g of Tinuvin ^® 770 DF (Ciba specialties GmbH, Lampertheim, DE) are then added, 10 min . stirred and the reaction mixture cooled to 60 ° C. The dispersion is carried out by adding

713.0 g water (20 ° C) at 60 ° C within 30 min. The stirring time at 40 ° C is 1 h. A storage-stable aqueous dispersion of the blocked polyisocyanate with a solids content of 27.3% is obtained.

Example 8:

147.4 g of a polyisocyanate containing biuret groups and based on 1,6-diisocyanate hexane (HDI) with an NCO content of 23.0% are initially charged at 40 ° C. Within 10 min. 121.0 g of polyether LB 25 (Bayer AG, Lev., DE, monofunctional polyether based on ethylene oxide / propylene oxide with an average molecular weight of 2250 (OHZ = 25) are metered in with stirring. The mixture is then heated

Reaction mixture at 90 ° C and stirred at this temperature until the theoretical NCO value is reached. After cooling to 65 ° C within 30 min. 62.8 g of butanone oxime added dropwise with stirring so that the temperature of the mixture does not exceed 80 ° C. The dispersion is carried out by adding 726.0 g of water (T = 20 ° C) at 60 ° C within 30 min. The stirring time at

40 ° C is 1 h. A storage-stable aqueous dispersion of the blocked polyisocyanate with a solids content of 30.0% is obtained.

Example 9:

13.5 g of polyether LB 25 (Bayer AG, Lev., DE, monofunctional polyether based on ethylene oxide / propylene oxide with an average molecular weight of 2250 (OHZ = 25)) and 122.6 g of N-tert-butylbenzylamine are introduced and under Stirring heated to 90 ° C. Then 193.0 of an isocyanurate group-containing polyisocyanate based on 1,6-diisocyanatohexane (HDI) with an NCO content of 21.8% within 30 minutes. added so that the temperature of the reaction mixture does not exceed 70 ° C. After adding 11.1 g of the abovementioned hydrazine adduct from 1 mol of hydrazine hydrate and 2 mol of propylene carbonate with a molecular weight of 236, the mixture is stirred at 70 ° C. until the theoretical NCO value is reached. Then 3.5 g of tinuvin ^® 770 DF (Ciba specialties GmbH,

Lampertheim, DE) at 70 ° C in 5 min. added and the reaction mixture further 5 min. touched. 24.6 g of the hydrophilizing agent KV 1386 (BASF AG, Ludwigshafen, DE) dissolved in 73.7 g of water are within 2 min. metered in and the reaction mixture for 15 min. further stirred. The dispersion by adding 736.4 g of water (T = 60 ° C) in 10 min. The stirring time is 2 hours. A storage-stable dispersion with a solids content of 27.6% is obtained.

Example 10:

963.0 g of a biuret group-containing polyisocyanate based on 1,6-diisocyanato-hexane (HDI) with an NCO content of 23.0% are mixed with 39.2 g of polyether LB 25

(Bayer AG, Lev., DE, monofunctional polyether based on ethylene oxide / propylene oxide with an average molecular weight of 2250 (OHZ = 25)) and _. 7.8 g of the above-mentioned hydrazine adduct from T mol of hydrazine hydrate and 2 mol of propylene carbonate with a molecular weight of 236 30 min. stirred at 100 ° C. Then within 20 min. 493.0 g of ε-caprolactam are added so that the temperature of the

Reaction mixture does not exceed 110 ° C. The mixture is stirred at 110 ° C. until the theoretical NCO value is reached and then cooled to 90 ° C. After adding 7.9 g of Tinuvin ^® 770 DF (Ciba Specialty GmbH, Lampertheim, DE) and stirring for 5 minutes. is within 2 min. a mixture of 152.5 g of the hydrophilizing agent KV 1386 (BASF AG, Ludwigshafen, DE) and 235.0 g

Water added and a further 7 min. stirred at a neutral temperature. This is followed by dispersion by adding 3341.4 g of water. After a subsequent stirring time of 4 h, a storage-stable aqueous dispersion with a solids content of 29.9% is obtained. Example 11:

192.6 g of a biuret group-containing polyisocyanate based on 1,6-diisocyanato-hexane (HDI) with an NCO content of 23.0% become monofunctional with 7.8 g of polyether LB 25 (Bayer AG, Leverkusen, DE) Polyether based on ethylene oxide propylene oxide with an average molecular weight of 2250 (OHZ = 25)) 30 min. stirred at 100 ° C. Then at 70 ° C within 30 min. 142.0 g of N-tert-butylbenzylamine are added so that the temperature of the reaction mixture does not exceed 75 ° C. The mixture is stirred at 75 ° C. until the theoretical NCO value is reached. Within 2 min. a mixture of 27.5 g of the hydrophilizing agent KV 1386 (BASF AG, Ludwigshafen, DE) and 46.8 g of water is metered in and a further 7 min. stirred at a neutral temperature. The dispersion is then carried out by adding 761.3 g of water. After a subsequent stirring time of 4 h, a storage-stable aqueous dispersion with a solids content of 28.0% is obtained.

Example 12:

154.1 g of a biuret group-containing polyisocyanate based on 1,6-diisocyanato-hexane (HDI) with an NCO content of 23.0% are mixed with 6.3 g of polyether LB 25

(Bayer AG, Lev., DE, monofunctional polyether based on ethylene oxide / propylene oxide with an average molecular weight of 2250 (OHZ = 25) was stirred for 30 minutes at 100 ° C. Then at 90 ° C. in the course of 20 minutes 6 g of butanone oxime are added so that the temperature of the reaction mixture does not exceed 110 ° C. The mixture is stirred at 100 ° C. until the theoretical NCO value is reached and then cooled to 90 ° C. After a stirring time of 5 min a mixture of 22.0 g of the hydrophilizing agent KV 1386 (BASF AG, Ludwigshafen, DE) and 37.5 g of water was metered in over the course of 2 minutes and the mixture was stirred for a further 7 minutes in a temperature-neutral manner. 5 g of water After a stirring time of 4 h, a storage-stable aqueous

Dispersion obtained with a solids content of 29.8%. Example 13:

963.0 g of a biuret group-containing polyisocyanate based on 1,6-diisocyanato-hexane (HDI) with an NCO content of 23.0% are mixed with 39.2 g of polyether LB 25

(Bayer AG, Lev., DE, monofunctional polyether based on ethylene oxide-propylene oxide with an average molecular weight of 2,250 (OHZ = 25) was stirred for 30 minutes at 100 ° C. 493.0 g of ε- Caprolactam is added so that the temperature of the reaction mixture does not exceed 110 ° C. The mixture is stirred at 110 ° C. until the theoretical NCO value is reached and then up

Cooled to 90 ° C. After a stirring time of 5 min. is within 2 min. a mixture of 152.5 g of the hydrophilizing agent KV 1386 (BASF AG, Ludwigshafen, DE) and 235.0 g of water are metered in and a further 7 min. stirred at a neutral temperature. This is followed by dispersion by adding 3325.1 g of water. After a subsequent stirring time of 4 h, a storage-stable aqueous

Obtained dispersion with a solids content of 30.0%.

Example 14:

To 343.20 g of an aliphatic polyisocyanate (Desmodur N 3300, Bayer AG,

Leverkusen) 99.12 g of PETIA (technical pentaerythritol triacrylate, Fa.UCB GmbH, Kerpen, DE) and 9.45 g of 1,6-hexanediol were added at 70 ° C. with stirring. A solution of 37.76 g of hydroxypivalic acid in 60.93 g of N-methylpyrrolidone was added dropwise at 70 ° C. in the course of 3 hours and the mixture was then stirred at 70 ° C. for 1 hour. Then 108.48 g of diisopropylamine were added dropwise at 70 ° C. in the course of 60 minutes and the mixture was subsequently stirred for 30 minutes. After this time, NCO groups were no longer detectable by IR spectroscopy. 883 g of deionized water at 70 ° C. were then added with vigorous stirring and stirring was continued for 1 hour. After cooling to room temperature with stirring, a dispersion having the following properties was obtained: Solids content: 40%

Viscosity (23 ° C): 200 mPas

Particle size (LKS): 89 nm

Example 15-17: Coating agents made from UN-curable polyurethane dispersions and water-dispersible blocked polyisocyanates for use in or as sizes

The compositions of the sizes are described in Tables 1-4. The mechanical of the coating agent or the size is determined on free films which are produced as follows:

A release paper is placed in front of the rear roller in a film puller consisting of two polished rollers that can be set to an exact distance. With a feeler gauge, the distance between the paper and the front

Roller set. This distance corresponds to the film thickness (wet) of the resulting coating and can be adjusted to the desired level of each stroke. Coating can also be carried out consecutively in several strokes. To apply the individual coats, the products (aqueous formulations are previously brought to a viscosity of by adding ammonia / polyacrylic acid

4500 mPa s) poured onto the gap between the paper and the front roller, the release paper is pulled vertically downwards, whereby the corresponding film is formed on the paper. If several strokes are to be applied, each individual stroke is dried and the paper is reinserted.

The 100% modulus was determined according to DIΝ 53504 on films> 100 μm thick.

The film is stored under hydrolysis conditions in accordance with DIΝ EΝ 12280-3. The mechanics of these film samples are determined after storage for 24 hours under standard climatic conditions (20 ° C and 65% humidity) according to DTN 53504.

The UV curing process was carried out on a UV curing system from the company IST (Nürtingen, DE) with a gallium-doped UV lamp (type CK I) with an output of 80 W / cm lamp length at a feed rate of 2.5 m / min ,

The results of the tests of the mechanical properties of the free films prove that, depending on the drying conditions, different crosslinking mechanisms can be addressed selectively separately from one another depending on the drying conditions.

1. Conditions (comparison

• Dry at 20 ° C for 45 minutes

• Dry for 10 minutes at 80 ° C

Table 1: 500 μm wet film applied to release paper

nfA = non-volatile component

Mirox® AM = thickener (Stockhausen, Krefeld, DE)

2. Conditions (comparison)

• Dry at 20 ° C for 45 minutes

• Dry for 10 minutes at 80 ° C

• Dry at 150 ° C for 30 minutes

Table 2: 500 μm wet film applied to release paper

nfA ^: non-volatile component

Mirox® AM ^: Nerdicker (Stockhausen, Krefeld, DE) 3. Conditions (comparison)

• Dry at 20 ° C for 45 minutes

• Dry for 10 minutes at 80 ° C

• UN drying: 2.5 m / min 80 W

nfA = non-volatile component

Mirox® AM = Nerdicker (Stockhausen, Krefeld, DE) 4. Conditions (according to the invention)

• Dry at 20 ° C for 45 minutes

• Dry for 10 minutes at 80 ° C

• Dry at 150 ° C for 30 minutes

• UN drying: 2.5 m / min 80 W

Table 4: 500 μm wet film applied to release paper

nfA = non-volatile component

Mirox® AM = Nerdicker (Stockhausen, Krefeld, DE) All of the dispersions described in Examples 1-17 are suitable for use in sizes and, in particular, show excellent low tolerance to aminosilanes such as, for example, aminopropyltriethoxysilane (Al 100, Union Carbide, USA). To test for AI 100 low tolerance, a 10% aqueous solution with a pH of 5.5-6.5 (adjusted with 10% acetic acid) is first prepared. The prepared AI 100 solution is placed in a burette and 200 g of PUR dispersion (from Examples 1-17) are provided in a beaker with magnetic stirrers and placed on a magnetic stirrer. The pH of the dispersion is measured with stirring, 2 ml of AllOO solution are added dropwise and the pH is measured until it reaches a constant value. The process is then repeated until 10% of the solution (calculated on the total amount of PU dispersion) has been introduced into the PUR dispersion. After each addition of aminosilane Al 100 solution, the pH value is measured and documented. If an incompatibility between PUR dispersion and aminosilane AI 100 is observed during the addition, the test is stopped. Otherwise, the dispersion mixed with AI 100 is kept for 24 hours in order to observe any subsequent changes, such as coagulum formation. All of the dispersions described in Examples 1-17 passed the above-mentioned compatibility test.

Claims

claims

1. A process for the production of glass fiber reinforced plastics, characterized in that a size composition is applied to the glass fiber, the water is removed, then irradiation with high-energy radiation takes place and in a second step the sized glass fiber is introduced into the plastic and a thermal hardening is carried out at 150 to 300 ° C with the release of the polyisocyanate groups by deblocking.

2. A method for producing glass fiber reinforced plastics according to claim 1, characterized in that the size composition

(I) at least one water-dispersible or water-soluble blocked polyisocyanate (A),

(II) at least one free radical polymerizable group-containing polyurethane (B) with a content of Zerewitinoff-active hydrogen atoms from 0 to 0.53 mmol and

(III) contains an initiator (C) which can trigger free-radical polymerization.

3. Process for the production of glass fiber reinforced plastics according to

Claim 1 or 2, characterized in that the blocked polyisocyanate (A) is a reaction product

(AI) at least one polyisocyanate with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups, (A2) at least one ionic or potentially ionic and / or nonionic compound,

(A3) at least one blocking agent,

(A4) optionally one or more (cyclo) aliphatic mono- or polyamines with 1 to 4 amino groups in the molecular weight range 32 to 300,

(A5) optionally one or more polyhydric alcohols with 1 to 4 hydroxyl groups in the molecular weight range 50 to 250 and

(A6) optionally one or more compounds containing isocyanate-reactive and unsaturated groups.

4. A process for the production of glass fiber reinforced plastics according to one or more of claims 1 to 3, characterized in that the polyurethane (B) is a reaction product

(a) one or more di- or polyisocyanates,

(b1) one or more compounds having a hydrophilic effect with ionic and / or groups which can be converted into ionic groups and / or nonionic groups,

(b2) one or more compounds with free-radically polymerizable groups,

(b3) optionally one or more polyol compounds with an average molecular weight of 50 to 500, preferably 80 to 200 and a hydroxyl functionality greater than or equal to 2 and less than or equal to 3,

(b4) optionally one or more polyol compounds with an average molecular weight of 500 to 13000 g / mol, preferably 700 to 4000 g / mol with an average hydroxyl functionality of 1.5 to 2.5, preferably from 1.8 to 2.2, particularly preferably from 1.9 to 2.1,

(b5) optionally one or more di- or polyamines.